We report here the synthesis and photophysical study of a series of electron donor–acceptor molecules, in which electron-donating 4-methoxyphenoxy groups are attached to the 1,7-bay positions of four different perylene tetracarboxylic acid derivatives, namely, perylene tetraesters 1, perylene monoimide diesters 2, perylene bisimides 3, and perylene monobenzimidazole monoimides 4. These perylene derivatives are used because of their increasing order of electron-accepting capability upon moving from 1 to 4. Two additional donor–acceptor molecules are synthesized by linking electron-donating 4-methoxyphenyl groups to the imide position of perylene monoimide diester 2 and perylene bisimide 3. The motivation for this study is to achieve a good control over the photoinduced charge-transfer (CT) process in perylene-based systems by altering the position of electron donors and tuning the electron deficiency of perylene core. A comprehensive study of the photophysical properties of these molecules has shown a highly systematic trend in the magnitude of CT as a function of increased electron deficiency of the perylene core and solvent polarity. Importantly, just by changing the attachment of electron-donating group from “bay” to “imide” position, we are able to block the CT process. This implies that the positioning of the electron donor at the perylene core strongly influences the kinetics of the photoinduced CT process. In these compounds, the CT process is characterized by the quenching of fluorescence and singlet excited-state lifetimes as compared to model compounds bearing non-electron-donating 4-tert-butylphenoxy groups. Transient absorption spectroscopy did not reveal spectra of CT states. This most likely implies that the CT state is not accumulated, because of the faster charge recombination.

We report the synthesis and excited-state dynamics of a series of five bichromophoric light-harvesting antenna systems, which are capable of efficient harvesting of solar energy in the spectral range of 350–580 nm. These antenna systems have been synthesized in a modular fashion by the covalent attachment of blue light absorbing naphthalene monoimide energy donors (D1, D2, and D3) to green light absorbing perylene-3,4,9,10-tetracarboxylic acid derived energy acceptors, 1,7-perylene-3,4,9,10-tetracarboxylic tetrabutylester (A1), 1,7-perylene-3,4,9,10-tetracarboxylic monoimide dibutylester (A2), and 1,7-perylene-3,4,9,10-tetracarboxylic bisimide (A3). The energy donors have been linked at the 1,7-bay-positions of the perylene derivatives, thus leaving the peri positions free for further functionalization and device construction. A highly stable and rigid structure, with no electronic communication between the donor and acceptor components, has been realized via an all-aromatic non-conjugated phenoxy spacer between the constituent chromophores. The selection of donor naphthalene derivatives for attachment with perylene derivatives was based on the effective matching of their respective optical properties to achieve efficient excitation energy transfer (EET) by the Förster mechanism. A comprehensive study of the excited-state dynamics, in toluene, revealed quantitative and ultrafast (ca. 1 ps) intramolecular EET from donor naphthalene chromophores to the acceptor perylenes in all the studied systems. Electron transfer from the donor naphthalene chromophores to the acceptor perylenes has not been observed, not even for antenna systems in which this process is thermodynamically allowed. Due to the combination of an efficient and fast energy transfer along with broad absorption in the visible region, these antenna systems are promising materials for solar-to-electric and solar-to-fuel devices.

Nucleophilic aromatic substitution reactions on 1,7-dibromoperylene-3,4,9,10-tetracarboxylic monoimide dibutylester, using phenol and pyrrolidine reagents, have been exploited to synthesize perylenes with four different substituents at the perylene core. The first substitution is always regiospecific at the imide-activated 7-position. A second substitution reaction does not always replace the bromine at C-1, but may replace a phenol substituent at the highly activated 7-position. Exploiting this reactivity pattern, a “mixed” 1,7-diphenoxy, 1,7-dipyrrolidinyl, and two 1-phenoxy-7-pyrrolidinyl derivatives have been synthesized.

Perylene-3,4,9,10-tetracarboxylic tetraester-based fluorescent PET probes with aniline receptors attached either at the peri- or the bay-positions have been synthesized. By attaching aniline receptors at the bay position, pH-sensitive “light-up” probes, with fluorescence quantum yields ΦF > 0.75 and fluorescent enhancements FE > 500 in ethanol, have been obtained.

A robust and scalable procedure to obtain pure 1,6,7,12-tetrachloroperylene-3,4,9,10-tetracarboxy bisanhydride, a highly valuable synthon, has been developed via synthesis of a novel intermediate compound 1,6,7,12-perylene-3,4,9,10-tetracarboxy tetrabutylester.

A fluorescent polyelectrolyte, poly(allylamine hydrochloride) (PAH) functionalised with the 7-amino-quinolinium chromophore, has been synthesized for the visualization of latent fingerprints. Exposing fingerprints to pH neutral, dilute aqueous solutions of this polymer results in bright green fluorescent images, which are clearly visible to the naked eye.

The perylene derivative 1,7-dibromoperylene-3,4,9,10-tetracarboxylic tetrabutylester has been obtained in regioisomerically pure form, by employing a highly efficient, scalable, and robust synthesis starting from commercially available perylene-3,4,9,10-tetracarboxylic bisanhydride. Subsequently, this compound is utilized for the synthesis of extremely valuable and versatile regioisomerically pure intermediates, namely, 1,7-dibromoperylene-3,4,9,10-tetracarboxylic dibutylester monoanhydride, 1,7-dibromoperylene-3,4,9,10-tetracarboxylic bisanhydride, and 1,7-dibromoperylene monoimid monoanhydride. These compounds possess at least one anhydride functionality in addition to the 1,7 bromo substituents and thus allow for a virtually limitless attachment of substituents both at the “peri” and the “bay” positions. The intermediate 1,7-dibromoperylene monoimide monoanhydride is of special interest as it provides access to unsymmetrically imide-substituted 1,7-dibromoperylene derivatives, which are not accessible by previously known procedures. Finally, substitution of the 1,7 bromine atoms in the bay area by phenoxy groups, which is a generally applied reaction for 1,7-dibromoperylene bisimides, was proven to be equally effective for a 1,7-dibromoperylene tetraester and a 1,7-dibromoperylene diester monoimid.

We report on the formation of unprecedented “leek”-shaped aggregates of an anionic fluoroalkyl sulfonate surfactant (FS) and the supramolecular assembly of these aggregates into a disordered columnar phase (CS). The leeks are formed by wrapping of 2–4 FS–water bilayers of thickness 26–28 Å into 10–20 nm thick and >100 nm long structures, in the concentration regime of 63–70 wt % FS. A lamellar (Lα) lyotropic liquid-crystalline (LLC) phase forms at higher concentration, between 70 and 84 wt %. In the two LLC phases, the FS molecules were organized in an interdigitated or tilted fashion, or a combination of the two. Such a unique supramolecular self-assembly of amphiphiles has not been predicted nor observed before. This self-assembly behavior could be of interest to various fields like microencapsulation, nanomedicine, and membrane protein crystallization.

A fluorescent polyelectrolyte, poly(allylamine hydrochloride) (PAH) functionalised with the 7-amino-quinolinium chromophore, has been synthesized for the visualization of latent fingerprints. Exposing fingerprints to pH neutral, dilute aqueous solutions of this polymer results in bright green fluorescent images, which are clearly visible to the naked eye.

Perylene-3,4,9,10-tetracarboxylic tetraester-based fluorescent PET probes with aniline receptors attached either at the peri- or the bay-positions have been synthesized. By attaching aniline receptors at the bay position, pH-sensitive “light-up” probes, with fluorescence quantum yields ΦF > 0.75 and fluorescent enhancements FE > 500 in ethanol, have been obtained.